UV-absorbing vinylic monomers and uses thereof

ABSTRACT

Described herein are water-soluble UV-absorbing vinylic monomers and their uses in preparing UV-absorbing contact lenses capable of blocking ultra-violet (“UV”) radiation and optionally (but preferably) violet radiation with wavelengths from 380 nm to 440 nm, thereby protecting eyes to some extent from damages caused by UV radiation and potentially from violet radiation. This invention also provides a UV-absorbing contact lens.

This application claims the benefits under 35 USC § 119 (e) of U.S.provisional application No. 62/298,137 filed 22 Feb. 2016, hereinincorporated by reference in its entirety.

This invention is related to water-soluble vinylic monomers capable ofabsorbing ultra-violet (UV) radiation and optionally high-energy-violet(HEVL) radiation and their uses for producing hydrogel contact lensescapable of blocking ultra-violet (“UV”) radiation and optionally (butpreferably) violet radiation with wavelengths from 380 nm to 440 nm froma water-based hydrogel lens formulation.

BACKGROUND

Most commercially-available hydrogel contact lenses are producedaccording to a conventional cast molding technique involving use ofdisposable plastic molds and a mixture of vinylic monomers andcrosslinking agents. There are several disadvantages with theconventional cast-molding technique. For example, a traditionalcast-molding manufacturing process often includes lens extraction inwhich unpolymerized monomers must be removed from the lenses by using anorganic solvent. Use of organic solvents can be costly and is notenvironmentally friendly. In addition, disposable plastic moldsinherently have unavoidable dimensional variations, because, duringinjection-molding of plastic molds, fluctuations in the dimensions ofmolds can occur as a result of fluctuations in the production process(temperatures, pressures, material properties), and also because theresultant molds may undergo non-uniformly shrinking after the injectionmolding. These dimensional changes in the mold may lead to fluctuationsin the parameters of contact lenses to be produced (peak refractiveindex, diameter, basic curve, central thickness etc.) and to a lowfidelity in duplicating complex lens design.

The above described disadvantages encountered in a conventionalcast-molding technique can be overcome by using the so-calledLightstream Technology™ (CIBA Vision), which involves (1) a lens-formingcomposition being substantially free of monomers and comprising asubstantially-purified, water-soluble prepolymer withethylenically-unsaturated groups, (2) reusable molds produced in highprecision, and (3) curing under a spatial limitation of actinicradiation (e.g., UV), as described in U.S. Pat. Nos. 5,508,317,5,583,163, 5,789,464, 5,849,810, 6,800,225, and 8,088,313. Lensesproduced according to the Lightstream Technology™ can have highconsistency and high fidelity to the original lens design, because ofuse of reusable, high precision molds. In addition, contact lenses withhigh quality can be produced at relatively lower cost due to the shortcuring time, a high production yield, and free of lens extraction and inan environmentally friendly manner because of use of water as solventfor preparing lens formulations. However, the Lightstream Technology™has not been applied to make contact lenses capable of absorbingultra-violet (UV) lights (between 280 nm and 380 nm) and optionallyhigh-energy violet lights (HEVL) (between 380 nm and 440 nm), largelybecause commercially-available polymerizable UV-absorbing vinylicmonomers and those disclosed in U.S. Pat. Nos. 4,612,358, 4,528,311,4,716,234, 7,803,359, 8,153,703, 8,232,326, and 8,585,938 (hereinincorporated by reference in their entireties) are not water-soluble andcannot be used in the production of contact lenses from a water-basedlens formulation.

Therefore, there are still needs for a new water-soluble UV-absorbingvinylic monomer or a new water-soluble UV/HEVL-absorbing vinylic monomerfor making UV-absorbing or UV/HEVL-absorbing contact lenses from awater-based lens formulation.

SUMMARY

In one aspect, the invention provides an UV-absorbing vinylic monomercomprising a moiety of benzophenone or benzotriazole, one or morehydrophilic moieties for rendering the UV-absorbing vinylic monomerwater-soluble, and a (meth)acryloyl group.

In another aspect, the invention provides a method for producingUV-absorbing contact lenses from an aqueous lens formulation comprisingat least one water-soluble, UV-absorbing vinylic monomer of theinvention.

The invention provides in a further aspect hydrogel contact lensescomprising monomeric units of an UV-absorbing vinylic monomer of theinvention.

BRIEF DESCRIPTIONS OF DRAWINGS

FIG. 1 shows the UV-visible absorption spectra of a preferredwater-soluble UV-absorbing vinylic monomer of the invention in aprotected form (curve 1) and an unprotected form (curve 2).

FIG. 2 shows the UV-visible transmission spectra of contact lenses: 0 wt%—control contact lens prepared from a lens formulation having 0 wt % ofany UV-absorbing vinylic monomer; and 0.7 wt %—contact lens preparedfrom a lens formulation comprising about 0.7 wt % of a UV-absorbingvinylic monomer of the invention according to a preferred embodiment.

FIG. 3 shows the UV-visible transmission spectra of contact lenses: 0 wt%—control contact lens prepared from a lens formulation having 0 wt % ofany UV-absorbing vinylic monomer; and 1.5 wt %—contact lens preparedfrom a lens formulation comprising about 1.5 wt % of a UV-absorbingvinylic monomer of the invention according to a preferred embodiment.

FIG. 4 shows the UV-visible absorption spectra of a preferredwater-soluble UV-absorbing vinylic monomer of the invention in aprotected form (curve 1) and an unprotected form (curve 2).

FIG. 5 shows the UV-visible transmission spectra of contact lenses: 0 wt%—control contact lens prepared from a lens formulation having 0 wt % ofany UV-absorbing vinylic monomer; and 0.9 wt %—contact lens preparedfrom a lens formulation comprising about 0.9 wt % of a UV-absorbingvinylic monomer of the invention according to a preferred embodiment.

FIG. 6 shows the UV-visible transmission spectra of contact lenses: 0 wt%—control contact lens prepared from a lens formulation having 0 wt % ofany UV-absorbing vinylic monomer; and 1.4 wt %—contact lens preparedfrom a lens formulation comprising about 1.4 wt % of a UV-absorbingvinylic monomer of the invention according to a preferred embodiment.

DETAILED DESCRIPTION

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which this invention belongs. Generally, the nomenclatureused herein and the laboratory procedures are well known and commonlyemployed in the art. Conventional methods are used for these procedures,such as those provided in the art and various general references. Wherea term is provided in the singular, the inventors also contemplate theplural of that term. The nomenclature used herein and the laboratoryprocedures described below are those well-known and commonly employed inthe art.

“About” as used herein means that a number referred to as “about”comprises the recited number plus or minus 1-10% of that recited number.

“Optional” or “optionally” means that the subsequently described eventor circumstance can or cannot occur, and that the description includesinstances where the event or circumstance occurs and instances where itdoes not.

A “contact Lens” refers to a structure that can be placed on or within awearer's eye. A contact lens can correct, improve, or alter a user'seyesight, but that need not be the case.

As used in this application, the term “hydrogel” or “hydrogel material”refers to a crosslinked polymeric material which is insoluble in water,but can hold at least 10 percent by weight of water in itsthree-dimensional polymer networks (i.e., polymer matrix) when it isfully hydrated.

A “vinylic monomer” refers to a compound that has one soleethylenically-unsaturated group and is soluble in a solvent.

The term “soluble”, in reference to a compound or material in a solvent,means that the compound or material can be dissolved in the solvent togive a solution with a concentration of at least about 0.1% by weight atroom temperature (i.e., from about 20° C. to about 30° C.).

The term “insoluble”, in reference to a compound or material in asolvent, means that the compound or material can be dissolved in thesolvent to give a solution with a concentration of less than 0.005% byweight at room temperature (as defined above).

The term “ethylenically unsaturated group” is employed herein in a broadsense and is intended to encompass any groups containing at leastone >C═C< group. Exemplary ethylenically unsaturated groups includewithout limitation (meth)acryloyl

allyl, vinyl

1-methylethenyl

styrenyl, or the likes.

The term “(meth)acryloylamido group” refers to a radical of

in which Rº is hydrogen or a C₁-C₆ alkyl.

The term “(meth)acrylamide” refers to methacrylamide and/or acrylamide.

The term “(meth)acrylate” refers to methacrylate and/or acrylate.

A “hydrophilic vinylic monomer”, as used herein, refers to a vinylicmonomer which can be polymerized to form a homopolymer that iswater-soluble or can absorb at least 10 percent by weight of water.

A “hydrophobic vinylic monomer” refers to a vinylic monomer which can bepolymerized to form a homopolymer that is insoluble in water and canabsorb less than 10 percent by weight of water.

“UVA” refers to radiation occurring at wavelengths between 315 and 380nanometers; “UVB” refers to radiation occurring between 280 and 315nanometers; “Violet” refers to radiation occurring at wavelengthsbetween 380 and 440 nanometers.

“UVA transmittance” (or “UVA % T”), “UVB transmittance” or “UVB % T”,and “violet-transmittance” or “Violet % T” are calculated by thefollowing formula

${{UVA}\mspace{14mu}\%\mspace{14mu} T} = {\frac{{Average}\mspace{14mu}\%\mspace{14mu}{Transmission}\mspace{14mu}{between}\mspace{14mu} 315\mspace{14mu}{and}\mspace{14mu} 380\mspace{14mu}{nm}}{{Luminescence}\mspace{14mu}\%\mspace{14mu} T} \times 100}$${{UVB}\mspace{14mu}\%\mspace{14mu} T} = {\frac{{Average}\mspace{14mu}\%\mspace{14mu}{Transmission}\mspace{14mu}{between}\mspace{14mu} 280\mspace{14mu}{and}\mspace{14mu} 315\mspace{14mu}{nm}}{{Luminescence}\mspace{14mu}\%\mspace{14mu} T} \times 100}$${{Violet}\mspace{14mu}\%\mspace{14mu} T} = {\frac{{Average}\mspace{14mu}\%\mspace{14mu}{Transmission}\mspace{14mu}{between}\mspace{14mu} 380\mspace{14mu}{and}\mspace{14mu} 440\mspace{14mu}{nm}}{{Luminescence}\mspace{14mu}\%\mspace{14mu} T} \times 100}$in which Luminescence % T is the ratio of luminous flux transmitted bythe lens to the incident luminous flux (ISO 13666:1998).

As used in this application, the term “macromer” or “prepolymer” refersto a medium and high molecular weight compound or polymer that containstwo or more ethylenically unsaturated groups. Medium and high molecularweight typically means average molecular weights greater than 700Daltons.

As used in this application, the term “vinylic crosslinker” refers to acompound having at least two ethylenically unsaturated groups. A“vinylic crosslinking agent” refers to a vinylic crosslinker having amolecular weight of about 700 Daltons or less.

As used in this application, the term “polymer” means a material formedby polymerizing/crosslinking one or more monomers or macromers orprepolymers.

As used in this application, the term “molecular weight” of a polymericmaterial (including monomeric or macromeric materials) refers to theweight-average molecular weight unless otherwise specifically noted orunless testing conditions indicate otherwise.

The term “alkyl” refers to a monovalent radical obtained by removing ahydrogen atom from a linear or branched alkane compound. An alkyl group(radical) forms one bond with one other group in an organic compound.

The term “alkylene divalent group” or “alkylene diradical” or “alkyldiradical” interchangeably refers to a divalent radical obtained byremoving one hydrogen atom from an alkyl. An alkylene divalent groupforms two bonds with other groups in an organic compound.

The term “alkyl triradical” refers to a trivalent radical obtained byremoving two hydrogen atoms from an alkyl. A alkyl triradical formsthree bonds with other groups in an organic compound.

The term “alkoxy” or “alkoxyl” refers to a monovalent radical obtainedby removing the hydrogen atom from the hydroxyl group of a linear orbranched alkyl alcohol. An alkoxy group (radical) forms one bond withone other group in an organic compound.

In this application, the term “substituted” in reference to an alkyldiradical or an alkyl radical means that the alkyl diradical or thealkyl radical comprises at least one substituent which replaces onehydrogen atom of the alkyl diradical or the alkyl radical and isselected from the group consisting of hydroxy (—OH), carboxy (—COOH),—NH₂, sulfhydryl (—SH), C₁-C₄ alkyl, C₁-C₄ alkoxy, C₁-C₄ alkylthio(alkyl sulfide), C₁-C₄ acylamino, C₁-C₄ alkylamino, di-C₁-C₄ alkylamino,halogen atom (Br or Cl), and combinations thereof.

A “photoinitiator” refers to a chemical that initiates free radicalcrosslinking/polymerizing reaction by the use of light.

In this application, a “UV-absorbing vinylic monomer” refers to avinylic monomer comprising an ethylenically-unsaturated group and anUV-absorbing moiety (benzophenone or benzotriazole moiety) which canabsorb or screen out UV radiation in the range from 200 nm to 400 nm asunderstood by a person skilled in the art.

A “spatial limitation of actinic radiation” refers to an act or processin which energy radiation in the form of rays is directed by, forexample, a mask or screen or combinations thereof, to impinge, in aspatially restricted manner, onto an area having a well-definedperipheral boundary. A spatial limitation of UV/visible radiation isobtained by using a mask or screen having a radiation (e.g., UV and/orvisible light) permeable region, a radiation (e.g., UV and/or visiblelight) impermeable region surrounding the radiation-permeable region,and a projection contour which is the boundary between theradiation-impermeable and radiation-permeable regions, as schematicallyillustrated in the drawings of U.S. Pat. No. 6,800,225 (FIGS. 1-11), andU.S. Pat. No. 6,627,124 (FIGS. 1-9), U.S. Pat. No. 7,384,590 (FIGS.1-6), and U.S. Pat. No. 7,387,759 (FIGS. 1-6), all of which areincorporated by reference in their entireties. The mask or screen allowsto spatially projects a beam of radiation (e.g., UV radiation and/orvisible radiation) having a cross-sectional profile defined by theprojection contour of the mask or screen. The projected beam ofradiation (e.g., UV radiation and/or visible radiation) limits radiationimpinging on a lens formulation located in the path of the projectedbeam from the first molding surface to the second molding surface of amold. The resultant contact lens comprises an anterior surface definedby the first molding surface, an opposite posterior surface defined bythe second molding surface, and a lens edge defined by the sectionalprofile of the projected UV and/or visible beam (i.e., a spatiallimitation of radiation). The radiation used for the crosslinking isradiation energy, especially UV radiation (and/or visible radiation),gamma radiation, electron radiation or thermal radiation, the radiationenergy preferably being in the form of a substantially parallel beam inorder on the one hand to achieve good restriction and on the other handefficient use of the energy.

The term “modulus” or “elastic modulus” in reference to a contact lensor a material means the tensile modulus or Young's modulus which is ameasure of the stiffness of a contact lens or a material. The moduluscan be measured using a method in accordance with ANSI Z80.20 standard.A person skilled in the art knows well how to determine the elasticmodulus of a silicone hydrogel material or a contact lens. For example,all commercial contact lenses have reported values of elastic modulus.

In general, the invention is directed to a class of UV-absorbing vinylicmonomers which are soluble in water due to the presence of one or morehydrophilic moieties, and can be used, in a water-based hydrogel lensformulation for making UV-absorbing hydrogel contact lenses, inparticularly, according to the Lightstream Technology™. Any unreactedUV-absorbing vinylic monomer can be efficiently removed by water or anaqueous solution as extraction solvent, if necessary.

In one aspect, the present invention provides a UV-absorbing vinylicmonomer of any one of formula (I) to (VII)

in which:

-   -   Rº is H, CH₃ or C₂H₅;    -   R₁, R₂ and R₂′ independent of one other are H, CH₃, CCl₃, CF₃,        Cl, Br, OH, OCH₃, or NR′R″ in which R′ and R″ independent of        each other are H or C₁-C₄ alkyl;    -   R₁′ independent of each other are H, CH₃, CCl₃, CF₃, Cl, Br, OH,        OCH₃, SO₃H, SO₃Na, or NR′R″ in which R′ and R″ independent of        each other are H or C₁-C₄ alkyl;    -   R₃ and R₄ independent of each other are H or a first hydrophilic        group which is *—CH₂—(OC₂H₄)_(n1)—OCH₃, *—CH₂—(OC₂H₄)_(n1)—OH,

-   -   provided that at least one of R₃ and R₄ is the first hydrophilic        group;    -   R₅ is H, *—COOH, *—CONH—C₂H₄—(OC₂H₄)_(n1)—OCH₃, or        *—CONH—C₂H₄—(OC₂H₄)_(n1)—OH;    -   one of R₆ and R₇ is H or a second hydrophilic group which is        *—CH₂—(OC₂H₄)_(n1)—OCH₃, *—CH₂—(OC₂H₄)_(n1)—OH,

-   -   while the other of R₆ and R₇ is

-   -   R₈ is CH₃, C₂H₅,

-   -   R₉ is SO₃Na,

-   -   R₉′ is H, SO₃Na,

-   -   R₁₀ is methyl or ethyl;    -   L1 is a direct bond or a linkage of

-   -   L2 is a linkage of *—CH₂—*, *—C₂H₄—*, *—C₃H₆—*, *—C₃H₆—S—C₂H₄—*,        *—C₃H₆—S—C₃H₆—*, or

-   -   X1 is O or NRº; and    -   Y₁, Y₂, and Y₃ independent of one another are a C₂-C₄ alkylene        divalent radical;    -   Q1, Q2, and Q3 independent of one another are a        (meth)acryloylamido or (meth)acryloyloxy group;    -   m1 is zero or 1, provided that if m1 is zero, then Q₂ is a        (meth)acryloylamido group; and    -   n1 is an integer of 2 to 20 (preferably 3 to 15, more preferably        4 to 10).

Preferred examples of a UV-absorbing vinylic monomer of formula (I)include without limitation:

in which: Q₁ is (meth)acryloylamido or (meth)acryloyloxy group; Y₁ is anethylene or propylene divalent radical; R₁ and R₂ independent of eachother are H, CH₃, CCl₃, CF₃, Cl, Br, OH, OCH₃, or NR′R″ in which R′ andR″ independent of each other are H, methyl or ethyl.

Preferred examples of a UV-absorbing vinylic monomer of formula (II)include without limitation:

in which: Q₁ is (meth)acryloylamido or (meth)acryloyloxy group; Y₁ is anethylene or propylene divalent radical; R₁ and R₂ independent of eachother are CH₃, CCl₃, CF₃, Cl, Br, NR′R″, OH, or OCH₃; R′ and R″independent of each other are H, methyl or ethyl; R₃ and R₄ independentof each other are *—CH₂—(OC₂H₄)_(n1)—OCH₃, *—CH₂—(OC₂H₄)_(n1)—OH,

R₁₀ is methyl or ethyl.

Preferred examples of a UV-absorbing vinylic monomer of formula (III)include without limitation:

in which: Q₁ is (meth)acryloylamido or (meth)acryloyloxy group; Y₁ is anethylene or propylene divalent radical; R₁ and R₂ independent of eachother are CH₃, CCl₃, CF₃, Cl, Br, NR′R″OH, or OCH₃; in which R′ and R″independent of each other are H or C₁-C₄ alkyl; R₈ is CH₃, C₂H₅,

R₁₀ is methyl or ethyl.

Preferred examples of a UV-absorbing vinylic monomer of formula (IV) or(V) include without limitation:

in which R₁′ is H, CH₃, CCl₃, CF₃, Cl, Br, NR′R″ in which R′ and R″independent of each other are H or C₁-C₄ alkyl, OH, or OCH₃; Q₂ is(meth)acryloylamido or (meth)acryloyloxy group; Y₂ is an ethylene orpropylene divalent radical.

Preferred examples of a UV-absorbing vinylic monomer of formula (VI) or(VII) include without limitation:

in which R₁′ is H, CH₃, CCl₃, CF₃, Cl, Br, F, OH, or OCH₃, NR′R″ inwhich R′ and R″ independent of each other are H or C₁-C₄ alkyl, R₈ isCH₃, C₂H₅,

R₁₀ is methyl or ethyl; Q₃ is (meth)acryloylamido or (meth)acryloyloxygroup; Y₃ is an ethylene or propylene divalent radical.

A UV-absorbing vinylic monomer of formula (I) defined above can beprepared according to procedures illustrated in Scheme 1:

It is understood that in the 2^(nd) step of Scheme 1 or 2 above, avinylic monomer of H₂N—Y₁-Q₁ (as defined above) can be substituted withanother vinylic monomer of HNRº—Y₁-Q₁ (as defined above) in which Rº isCH₃ or C₂H₅ for making other UV-absorbing vinylic monomers of formula(I) or (II). Exemplary vinylic monomers of HNRº—Y₁-Q₁ (as defined above)include without limitation 2-(methylamino)ethyl (meth)acrylate,2-(methylamino)ethyl (meth)acrylamide, N-Methyl-N-[2-(methylamino)ethyl](meth)acrylamide, ethylaminoethyl (meth)acrylate, ethylaminoethyl(meth)acrylamide, methylaminopropyl (meth)acrylate, methylaminopropyl(meth)acrylamide, ethylaminopropyl (meth)acrylate, and ethylaminopropyl(meth)acrylamide.

A UV-absorbing vinylic monomer of formula (II) defined above can beprepared according to procedures illustrated in Scheme 2:

It is understood that in the 2^(nd) step of Scheme 2 above, a vinylicmonomer of H₂N—Y₁-Q₁ (as defined above) can be substituted with anothervinylic monomer of HNRº—Y₁-Q₁ (as defined above) in which Rº is CH₃ orC₂H₅ for making other UV-absorbing vinylic monomers of formula (II). Itis also understood that the 3^(rd) step of Scheme 2 can be altered toform a phosphocholine group by reacting an alkyl alkylene phosphate(e.g., methyl ethylene phosphate, ethyl ethylene phosphate, methylpropylene phosphate, or ethyl propylene phosphate), instead of1,3-propane sultone, under conditions known to a person skilled in theart (Makromol. Chem., Rapid Commun. 3, 457-459 (1982), hereinincorporated by reference in its entirety).

A UV-absorbing vinylic monomer of formula (III) defined above can beprepared according to procedures illustrated in Scheme 3:

It is also understood that Scheme 3 can be modified by replacing avinylic monomer of (CH₃)₂N—Y₁-Q₁ can be substituted with another vinylicmonomer of HNRº—Y₁-Q₁ in which Rº is CH₃ or C₂H₅ and then by adding onestep of reacting the product of the 3^(rd) step with 1,3-propane sultoneor an alkyl alkylene phosphate (e.g., methyl ethylene phosphate, ethylethylene phosphate, methyl propylene phosphate, or ethyl propylenephosphate) under conditions known to a person skilled in the art to forma UV-absorbing vinylic monomer of formula (III) with R₈ is a radicalother than methyl.

Any 2-hydroxy-2′-carboxy benzophenones with substituents on either orboth benzene rings can be used in the preparation of a UV-absorbingvinylic monomer of formula (I), (II) or (III). A person knows how toprepare a 2-hydroxy-2′-carboxy benzophenones with substituents from asubstituted or unsubstituted phthalic anhydride and a substituted orunsubstituted phenol (see, e.g., U.S. Pat. No. 5,925,787, hereinincorporated in reference in its entirety).

It is understood that in the 2^(nd) step of Scheme 2 any 3- and4-substituted phthalic anhydride can be used to react with any mono- ordi-substituted phenol to obtain a UV-absorbing vinylic monomer offormula (I), (II) or (III). Various 3- and 4-substituted phthalicanhydrides are commercially available or can be prepared according tothe procedures described in J. Chem. Soc., Perkin Trans. (1977), 1:2030-2036 (herein incorporated by reference in its entirety).

A UV-absorbing vinylic monomer of formula (IV) or (V) defined above canbe prepared according to procedures illustrated in any one of Schemes 4to 7:

A UV-absorbing vinylic monomer of formula (VI) or (VII) defined abovecan be prepared according to procedures illustrated in Scheme 8 or 9:

Any benzotriazoles with substituents can be used in the preparation of avinylic monomer of any one of formula (IV) to (VII). A person knows howto prepare a benzotriazole with different substituents according to aknown procedure (see, e.g., U.S. Pat. No. 8,262,948, herein incorporatedin reference in its entirety).

A water-soluble UV-absorbing vinylic monomer of the invention describedabove can find particular uses in making UV-absorbing medical devices,preferably ophthalmic devices, more preferably intraocular lenses, evenmore preferably contact lenses.

In another aspect, the invention provides a method for producingUV-absorbing contact lenses, comprising the steps of: (1) obtaining alens formulation comprising (a) (from about 0.1% to about 4% by weightof, preferably from about 0.2% to about 3.0% by weight of, morepreferably from about 0.4% to about 2% by weight of, even morepreferably from about 0.6% to about 1.5% by weight of) a UV-absorbingvinylic monomer of any one of formula (I) to (VII) (as defined above),(b) (from about 0.1% to about 2.0% by weight of, preferably from about0.25% to about 1.75% by weight of, more preferably from about 0.5% toabout 1.5% by weight of, even more preferably from about 0.75% to about1.25% by weight of) at least free-radical initiator, and (c) at leastone polymerizable components selected from the group consisting of ahydrophilic vinylic monomer, a water-soluble silicone-free prepolymer, asilicone-containing prepolymer, a non-silicone hydrophobic vinylicmonomer, a siloxane-containing vinylic monomer, a siloxane-containingvinylic macromer, a vinylic crosslinking agent, and combinationsthereof; (2) introducing the lens formulation into a mold for making asoft contact lens, wherein the mold has a first mold half with a firstmolding surface defining the anterior surface of a contact lens and asecond mold half with a second molding surface defining the posteriorsurface of the contact lens, wherein said first and second mold halvesare configured to receive each other such that a cavity is formedbetween said first and second molding surfaces; and (3) curing thermallyor actinically the lens formulation in the mold to form the UV-absorbingcontact lens, wherein the formed UV-absorbing contact lens ischaracterized by having the UVB transmittance of about 10% or less(preferably about 5% or less, more preferably about 2.5% or less, evenmore preferably about 1% or less) between 280 and 315 nanometers and aUVA transmittance of about 30% or less (preferably about 20% or less,more preferably about 10% or less, even more preferably about 5% orless) between 315 and 380 nanometers and and optionally (but preferably)a Violet transmittance of about 60% or less, preferably about 50% orless, more preferably about 40% or less, even more preferably about 30%or less) between 380 nm and 440 nm.

In accordance with the invention, a free-radical initiator can be afree-radical thermal initiator or a free-radical photoinitiator.

Any thermal free-radical initiators can be used in the invention.Examples of suitable thermal initiators include, but are not limited to,2,2′-azobis (2,4-dimethylpentanenitrile), 2,2′-azobis(2-methylpropanenitrile), 2,2′-azobis (2-methylbutanenitrile), peroxidessuch as benzoyl peroxide, and the like. Preferably, the thermalinitiator is 2,2′-azobis(isobutyronitrile) (AIBN).

Any free-radical photoinitiators, which can absorb radiation in therange from 380 nm to 500 nm, can be used in the invention. Suitablephotoinitiators are benzoin methyl ether, diethoxyacetophenone, abenzoylphosphine oxide, 1-hydroxycyclohexyl phenyl ketone and Darocurand Irgacur types, preferably Darocur 1173® and Darocur 2959®,Germanium-based Norrish Type I photoinitiators. Examples ofbenzoylphosphine initiators includephenyl(2,4,6-trimethylbenzoyl)phosphinic acid and its salts,bis(2,4,6-trimethylbenzoyl)phosphinic acid and its salts,2,4,6-trimethylbenzoyldiphenylophosphine oxide;bis-(2,6-dichlorobenzoyl)-4-N-propylphenylphosphine oxide; andbis-(2,6-dichlorobenzoyl)-4-N-butylphenylphosphine oxide. Reactivephotoinitiators which can be incorporated, for example, into a macromeror can be used as a special monomer are also suitable. Examples ofreactive photoinitiators are those disclosed in EP 632 329, hereinincorporated by reference in its entirety. Most preferably,water-soluble Germanium-based Norrish Type I photoinitiators, which aredisclosed in copending U.S. patent application No. 62/169,722 filed Jun.2, 2015 (herein incorporated by reference in its entirety), are used inthe invention. The polymerization can then be triggered off by actinicradiation, for example, UV and/or visible light of a suitablewavelength. The spectral requirements can be controlled accordingly, ifappropriate, by addition of suitable photosensitizers.

Nearly any hydrophilic vinylic monomer can be used in the invention.Suitable hydrophilic vinylic monomers are, without this being anexhaustive list, N,N-dimethylacrylamide (DMA),N,N-dimethylmethacrylamide (DMMA), 2-acrylamidoglycolic acid,N-hydroxypropylacrylamide, N-hydroxyethyl acrylamide,N-[tris(hydroxymethyl)methyl]-acrylamide, N-vinylpyrrolidone (NVP),N-vinyl formamide, N-vinyl acetamide, N-vinyl isopropylamide,N-vinyl-N-methyl acetamide (VMA), N-methyl-3-methylene-2-pyrrolidone,1-methyl-5-methylene-2-pyrrolidone, 5-methyl-3-methylene-2-pyrrolidone,2-hydroxyethylmethacrylate (HEMA), 2-hydroxyethyl acrylate (HEA),hydroxypropyl acrylate, hydroxypropyl methacrylate,methoxyethylmethacrylate (i.e., ethylene glycol methyl ethermethacrylate, EGMA), trimethylammonium 2-hydroxy propylmethacrylatehydrochloride, aminopropyl methacrylate hydrochloride,dimethylaminoethyl methacrylate (DMAEMA), glycerol methacrylate (GMA), aC₁-C₄-alkoxy polyethylene glycol (meth)acrylate having a weight averagemolecular weight of up to 1500, polyethylene glycol (meth)acrylatehaving a weight average molecular weight of up to 1500, methacrylicacid, acrylic acid, and mixtures thereof.

Examples of water-soluble prepolymers free of silicone include withoutlimitation: a water-soluble crosslinkable poly(vinyl alcohol) prepolymerdescribed in U.S. Pat. Nos. 5,583,163 and 6,303,687; a water-solublevinyl group-terminated polyurethane prepolymer described in U.S. Pat.No. 6,995,192; derivatives of a polyvinyl alcohol, polyethyleneimine orpolyvinylamine, which are disclosed in U.S. Pat. No. 5,849,841; awater-soluble crosslinkable polyurea prepolymer described in U.S. Pat.Nos. 6,479,587 and 7,977,430; crosslinkable polyacrylamide;crosslinkable statistical copolymers of vinyl lactam, MMA and acomonomer, which are disclosed in U.S. Pat. No. 5,712,356; crosslinkablecopolymers of vinyl lactam, vinyl acetate and vinyl alcohol, which aredisclosed in U.S. Pat. No. 5,665,840; polyether-polyester copolymerswith crosslinkable side chains which are disclosed in U.S. Pat. No.6,492,478; branched polyalkylene glycol-urethane prepolymers disclosedin U.S. Pat. No. 6,165,408; polyalkylene glycol-tetra(meth)acrylateprepolymers disclosed in U.S. Pat. No. 6,221,303; crosslinkablepolyallylamine gluconolactone prepolymers disclosed in U.S. Pat. No.6,472,489; all of which are incorporated herein by references in theirentireties.

Any suitable of silicone-containing prepolymers with hydrophilicsegments and hydrophobic segments can be used in the invention. Examplesof such silicone-containing prepolymers include those described incommonly-owned U.S. Pat. Nos. 6,039,913, 7,091,283, 7,268,189 and7,238,750, 7,521,519; commonly-owned US patent application publicationNos. US 2008-0015315 A1, US 2008-0143958 A1, US 2008-0143003 A1, US2008-0234457 A1, US 2008-0231798 A1, US 2010-0296049 A1, and US2010-0298446 A1; all of which are incorporated herein by references intheir entireties.

A lens formulation of the invention can also comprise a non-siliconehydrophobic monomer (i.e., free of silicone). By incorporating a certainamount of non-silicone hydrophobic vinylic monomer in a lensformulation, the mechanical properties (e.g., modulus of elasticity) ofthe resultant polymer may be improved. Nearly any non-siliconehydrophobic vinylic monomer can be used in the actinically polymerizablecomposition for preparing the intermediary copolymer with pendant orterminal functional groups. Examples of preferred non-siliconehydrophobic vinylic monomers include methylacrylate, ethyl-acrylate,propylacrylate, isopropylacrylate, cyclohexylacrylate,2-ethylhexylacrylate, methylmethacrylate, ethylmethacrylate,propylmethacrylate, vinyl acetate, vinyl propionate, vinyl butyrate,vinyl valerate, styrene, chloroprene, vinyl chloride, vinylidenechloride, acrylonitrile, 1-butene, butadiene, methacrylonitrile, vinyltoluene, vinyl ethyl ether,perfluorohexylethyl-thio-carbonyl-aminoethyl-methacrylate, isobornylmethacrylate, trifluoroethyl methacrylate, hexafluoro-isopropylmethacrylate, hexafluorobutyl methacrylate.

Any suitable siloxane-containing vinylic monomers can be used in theinvention. Examples of preferred siloxane-containing vinylic monomersinclude without limitationN-[tris(trimethylsiloxy)silylpropyl]-(meth)acrylamide,N-[tris(dimethylpropylsiloxy)-silylpropyl]-(meth)acrylamide,N-[tris(dimethylphenylsiloxy)silylpropyl] (meth)acrylamide,N-[tris(dimethylethylsiloxy)silylpropyl] (meth)acrylamide,N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)-methylsilyl)propyloxy)propyl)-2-methylacrylamide;N-(2-hydroxy-3-(3-(bis(trimethylsilyloxy)-methylsilyl)propyloxy)propyl)acrylamide;N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)-methylsilyl)propyloxy)propyl]-2-methylacrylamide;N,N-bis[2-hydroxy-3-(3-(bis(trimethylsilyloxy)-methylsilyl)propyloxy)propyl]acrylamide;N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)-propyloxy)propyl)-2-methylacrylamide;N-(2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)-propyl)acrylamide;N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]-2-methylacrylamide;N,N-bis[2-hydroxy-3-(3-(tris(trimethylsilyloxy)silyl)propyloxy)propyl]acrylamide;N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]-2-methylacrylamide;N-[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)propyl]acrylamide;N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)-propyloxy)propyl]-2-methylacrylamide;N,N-bis[2-hydroxy-3-(3-(t-butyldimethylsilyl)propyloxy)-propyl]acrylamide;3-methacryloxy propylpentamethyldisiloxane,tris(trimethylsilyloxy)silylpropyl methacrylate (TRIS),(3-methacryloxy-2-hydroxypropyloxy)propylbis(trimethylsiloxy)-methylsilane),(3-methacryloxy-2-hydroxypropyloxy)propyltris(trimethylsiloxy)silane,3-methacryloxy-2-(2-hydroxyethoxy)-propyloxy)propylbis(trimethylsiloxy)methylsilane,N-2-methacryloxyethyl-O-(methyl-bis-trimethylsiloxy-3-propyl)silylcarbamate,3-(trimethylsilyl)-propylvinyl carbonate,3-(vinyloxycarbonylthio)propyl-tris(trimethyl-siloxy)silane,3-[tris(trimethyl-siloxy)silyl]propylvinyl carbamate,3-[tris(trimethylsiloxy)silyl] propyl allyl carbamate,3-[tris(trimethylsiloxy)silyl]propyl vinyl carbonate,t-butyldimethyl-siloxyethyl vinyl carbonate; trimethylsilylethyl vinylcarbonate, and trimethylsilylmethyl vinyl carbonate); monomethacrylatedor monoacrylated polydimethylsiloxanes of various molecular weight(e.g., mono-3-methacryloxypropyl terminated, mono-butyl terminatedpolydimethylsiloxane or mono-(3-methacryloxy-2-hydroxypropyloxy) propylterminated, mono-butyl terminated polydimethylsiloxane); mono-vinylcarbonate-terminated polydimethylsiloxanes; mono-vinylcarbamate-terminated polydimethylsiloxane;mono-methacrylamide-terminated polydimethylsiloxanes;mono-acrylamide-terminated polydimethylsiloxanes; carbosiloxane vinylicmonomers disclosed in U.S. Pat. Nos. 7,915,323 and 8,420,711, in USPatent Application Publication Nos. 2012/244088 and 2012/245249 (hereinincorporated by references in their entireties); combinations thereof.

Any suitable siloxane-containing vinylic macromers (i.e., crosslinkers)can be used in the invention. Examples of preferred siloxane-containingvinylic macromers (crosslinkers) are dimethacrylated or diacrylatedpolydimethylsiloxanes of various molecular weight; di-vinylcarbonate-terminated polydimethylsiloxanes; di-vinylcarbamate-terminated polydimethylsiloxane; di-methacrylamide-terminatedpolydimethylsiloxanes; di-acrylamide-terminated polydimethylsiloxanes;bis-3-methacryloxy-2-hydroxypropyloxypropyl polydimethylsiloxane;N,N,N′,N′-tetrakis(3-methacryloxy-2-hydroxypropyl)-alpha,omega-bis-3-aminopropyl-polydimethylsiloxane;polysiloxanylalkyl (meth)acrylic monomers; siloxane-containing macromerselected from the group consisting of Macromer A, Macromer B, MacromerC, and Macromer D described in U.S. Pat. No. 5,760,100 (hereinincorporated by reference in its entirety); chain-extended polysiloxabevinylic crosslinkers disclosed in US201008843A1 and US20120088844A1(herein incorporated by references in their entireties); the reactionproducts of glycidyl methacrylate with amino-functionalpolydimethylsiloxanes; hydroxyl-functionalized siloxane-containingvinylic monomers or macromers; polysiloxane-containing macromersdisclosed in U.S. Pat. Nos. 4,136,250, 4,153,641, 4,182,822, 4,189,546,4,343,927, 4,254,248, 4,355,147, 4,276,402, 4,327,203, 4,341,889,4,486,577, 4,543,398, 4,605,712, 4,661,575, 4,684,538, 4,703,097,4,833,218, 4,837,289, 4,954,586, 4,954,587, 5,010,141, 5,034,461,5,070,170, 5,079,319, 5,039,761, 5,346,946, 5,358,995, 5,387,632,5,416,132, 5,451,617, 5,486,579, 5,962,548, 5,981,675, 6,039,913, and6,762,264 (here incorporated by reference in their entireties);polysiloxane-containing macromers disclosed in U.S. Pat. Nos. 4,259,467,4,260,725, and 4,261,875 (herein incorporated by reference in theirentireties).

Examples of preferred vinylic cross-linking agents include withoutlimitation tetraethyleneglycol diacrylate, triethyleneglycol diacrylate,diethyleneglycol diacrylate, ethyleneglycol diacrylate,tetraethyleneglycol dimethacrylate, triethyleneglycol dimethacrylate,diethyleneglycol dimethacrylate, ethyleneglycol dimethacrylate,tetraethyleneglycol divinyl ether, triethyleneglycol divinyl ether,diethyleneglycol divinyl ether, ethyleneglycol divinyl ether,trimethylopropane trimethacrylate, pentaerythritol tetramethacrylate,bisphenol A dimethacrylate, vinyl methacrylate, ethylenediaminedimethyacrylamide, ethylenediamine diacrylamide, glyceroldimethacrylate, triallyl isocyanurate, triallyl cyanurate,allylmethacrylate, allylacrylate, N-allyl-methacrylamide,N-allyl-acrylamide,1,3-bis(methacrylamidopropyl)-1,1,3,3-tetrakis(trimethyl-siloxy)disiloxane,N,N′-methylenebisacrylamide, N,N′-methylenebismethacrylamide,N,N′-ethylenebisacrylamide, N,N′-ethylenebismethacrylamide,1,3-bis(N-methacrylamidopropyl)-1,1,3,3-tetrakis-(trimethylsiloxy)disiloxane,1,3-bis(methacrylamidobutyl)-1,1,3,3-tetrakis(trimethylsiloxy)disiloxane,1,3-bis(acrylamidopropyl)-1,1,3,3-tetrakis(trimethylsiloxy)-disiloxane,1,3-bis(methacryloxyethylureidopropyl)-1,1,3,3-tetrakis(trimethylsiloxy)disiloxane,and combinations thereof. A preferred cross-linking agent istetra(ethyleneglycol) diacrylate, tri(ethyleneglycol) diacrylate,ethyleneglycol diacrylate, di(ethyleneglycol) diacrylate,methylenebisacrylamide, triallyl isocyanurate, or triallyl cyanurate.The amount of a cross-linking agent used is expressed in the weightcontent with respect to the total polymer and is preferably in the rangefrom about 0.05% to about 3% (more preferably from about 0.1% to about2%).

A lens formulation of the invention can further comprise visibilitytinting agents (e.g., D&C Blue No. 6, D&C Green No. 6, D&C Violet No. 2,carbazole violet, certain copper complexes, certain chromium oxides,various iron oxides, phthalocyanine green, phthalocyanine blue, titaniumdioxides, or mixtures thereof), antimicrobial agents (e.g., silvernanoparticles), a bioactive agent (e.g., a drug, an amino acid, apolypeptide, a protein, a nucleic acid, 2-pyrrolidone-5-carboxylic acid(PCA), an alpha hydroxyl acid, linoleic and gamma linoleic acids,vitamins, or any combination thereof), leachable lubricants (e.g., anon-crosslinkable hydrophilic polymer having an average molecular weightfrom 5,000 to 500,000, preferably from 10,000 to 300,000, morepreferably from 20,000 to 100,000 Daltons), leachable tear-stabilizingagents (e.g., a phospholipid, a monoglyceride, a diglyceride, atriglyceride, a glycolipid, a glyceroglycolipid, a sphingolipid, asphingo-glycolipid, a fatty acid having 8 to 36 carbon atoms, a fattyalcohol having 8 to 36 carbon atoms, or a mixture thereof), and thelike, as known to a person skilled in the art.

In a preferred embodiment, the lens formulation is a water-based lensformulation which comprises one or more water-solubleactinically-crosslinkable poly(vinyl alcohol) prepolymer. Preferably, awater-soluble, actinically-crosslinkable polyvinyl alcohol prepolymercomprises repeating units of vinyl alcohol

and repeating units of formula (VIII)

in which:

-   -   R₁₁ is hydrogen or C₁-C₆ alkyl (preferably hydrogen or C₁-C₄        alkyl, more preferably hydrogen or methyl or ethyl, even more        preferably hydrogen or methyl);    -   R₁₂ is an ethylenically unsaturated group of

-   -   in which q1 and q2 independently of each another are zero or        one, and R₁₆ and R₁₇ independently of each another are a C₂-C₈        alkylene divalent radical, R₁₈ is C₂-C₈ alkenyl;    -   R₁₃ can be hydrogen or a C₁-C₆ alkyl group (preferably        hydrogen); and    -   R₁₄ is a C₁-C₆ alkylene divalent radical (preferably a C₁-C₄        alkylene divalent radical, more preferably methylene or butylene        divalent radical, even more preferably methylene divalent        radical).

In another preferred embodiment, a lens formulation comprises awater-soluble silicone-containing prepolymer. Examples of water-solublesilicone-containing prepolymers include without limitation thosedisclosed in U.S. Pat. No. 9,187,601 (herein incorporated by referencein its entirety).

A “water-based lens formulation” refers to a polymerizable compositionwhich comprises water as solvent or a solvent mixture comprising atleast about 60% (preferably at least about 80%, more preferably at leastabout 90%, even more preferably at least about 95%, most preferably atleast about 98%) by weight of water relative to the total amount of thesolvent mixture and polymerizable/crosslinkable components, and whichcan be cured (i.e., polymerized and/or crosslinked) thermally oractinically to obtain a crosslinked/polymerized polymeric material.

It is understood that the amount of the UV-absorbing vinylic monomerpresent in the lens formulation is sufficient to render a resultantcontact lens, which is obtained from the curing of the lens formulation,ability of blocking or absorbing (i.e., the inverse of transmittance) atleast 90% (preferably at least about 95%, more preferably at least about97.5%, even more preferably at least about 99%) of UVB (between 280 and315 nanometers), at least 70% (preferably at least about 80%, morepreferably at least about 90%, even more preferably at least about 95%)of UVA transmittance (between 315 and 380 nanometers), and optionally(but preferably) at least 30% (preferably at least about 40%, morepreferably at least about 50%, even more preferably at least about 60%)of violet light between 380 nm and 440 nm, which impinge on the lens.

In accordance with the invention, a lens formulation can be awater-based lens formulation, an organic solvent-based lens formulation,or a solventless formulation.

A lens formulation can be prepared by dissolving all of the desirablecomponents in water, a mixture of water and an organic solvent, anorganic solvent, or a mixture of two or more organic solvent, or byblending all polymerizable components without any solvent, as known to aperson skilled in the art.

In another preferred embodiment, the lens formulation comprises anUV-absorbing vinylic monomer of any one of formula (I) to (VII) in whichQ1, Q2, and Q3 are a (meth)acryloylamido group (preferably anacryloylamido group). By having a (meth)acryloylamido group (preferablyan acryloylamido group), a relatively-short curing time (e.g., less than100 seconds, preferably less than 75 seconds, more preferably less than50 second, even more preferably about 30 seconds or less) can beachieved.

Lens molds for making contact lenses are well known to a person skilledin the art. Methods of manufacturing mold sections for cast-molding acontact lens are generally well known to those of ordinary skill in theart. The process of the present invention is not limited to anyparticular method of forming a mold. In fact, any method of forming amold can be used in the present invention. The first and second moldhalves can be formed through various techniques, such as injectionmolding or lathing. Examples of suitable processes for forming the moldhalves are disclosed in U.S. Pat. No. 4,444,711 to Schad; U.S. Pat. No.4,460,534 to Boehm et al.; U.S. Pat. No. 5,843,346 to Morrill; and U.S.Pat. No. 5,894,002 to Boneberger et al., which are also incorporatedherein by reference. Virtually all materials known in the art for makingmolds can be used to make molds for making contact lenses. For example,polymeric materials, such as polyethylene, polypropylene, polystyrene,PMMA, Topas® COC grade 8007-S10 (clear amorphous copolymer of ethyleneand norbornene, from Ticona GmbH of Frankfurt, Germany and Summit,N.J.), or the like can be used. Other materials that allow UV lighttransmission could be used, such as quartz glass and sapphire.

Preferably, a reusable mold suitable for spatial limitation of radiationis used in the invention, the projected beam of radiation (e.g.,radiation from the light source including the light in the region of 360nm to 550 nm) limits radiation (e.g., UV radiation) impinging on themixture of the lens-forming materials located in the path of theprojected beam from the first molding surface to the second moldingsurface of the reusable mold. The resultant contact lens comprises ananterior surface defined by the first molding surface, an oppositeposterior surface defined by the second molding surface, and a lens edge(with sharp edge and high quality) defined by the sectional profile ofthe projected radiation beam (i.e., a spatial limitation of radiation).Examples of reusable molds suitable for spatial limitation of radiationinclude without limitation those disclosed in U.S. Pat. Nos. 6,627,124,6,800,225, 7,384,590, and 7,387,759, which are incorporated by referencein their entireties.

For example, a preferred reusable mold comprises a first mold halfhaving a first molding surface and a second mold half having a secondmolding surface. The two mold halves of the preferred reusable mold arenot touching each other, but there is a thin gap of annular designarranged between the two mold halves. The gap is connected to the moldcavity formed between the first and second molding surfaces, so thatexcess mixture can flow into the gap. It is understood that gaps withany design can be used in the invention.

In a preferred embodiment, at least one of the first and second moldingsurfaces is permeable to a crosslinking radiation. More preferably, oneof the first and second molding surfaces is permeable to a crosslinkingradiation while the other molding surface is poorly permeable to thecrosslinking radiation.

The reusable mold preferably comprises a mask which is fixed,constructed or arranged in, at or on the mold half having theradiation-permeable molding surface. The mask is impermeable or at leastof poor permeability compared with the permeability of theradiation-permeable molding surface. The mask extends inwardly right upto the mold cavity and surrounds the mold cavity so as to screen allareas behind the mask with the exception of the mold cavity.

The mask may preferably be a thin chromium layer, which can be producedaccording to processes as known, for example, in photo and UVlithography. Other metals or metal oxides may also be suitable maskmaterials. The mask can also be coated with a protective layer, forexample of silicon dioxide if the material used for the mold or moldhalf is quartz.

Alternatively, the mask can be a masking collar made of a materialcomprising a UV/visible light-absorber and substantially blocks curingenergy therethrough as described in U.S. Pat. No. 7,387,759(incorporated by reference in its entirety). In this preferredembodiment, the mold half with the mask comprises a generally circulardisc-shaped transmissive portion and a masking collar having an innerdiameter adapted to fit in close engagement with the transmissiveportion, wherein said transmissive portion is made from an opticallyclear material and allows passage of curing energy therethrough, andwherein the masking collar is made from a material comprising alight-blocker and substantially blocks passage of curing energytherethrough, wherein the masking collar generally resembles a washer ora doughnut, with a center hole for receiving the transmissive portion,wherein the transmissive portion is pressed into the center opening ofthe masking collar and the masking collar is mounted within a bushingsleeve.

Reusable molds can be made of quartz, glass, sapphire, CaF₂, a cyclicolefin copolymer (such as for example, Topas® COC grade 8007-S10 (clearamorphous copolymer of ethylene and norbornene) from Ticona GmbH ofFrankfurt, Germany and Summit, N.J., Zeonex® and Zeonor® from ZeonChemicals LP, Louisville, Ky.), polymethylmethacrylate (PMMA),polyoxymethylene from DuPont (Delrin), Ultem® (polyetherimide) from G.E.Plastics, PrimoSpire®, etc. Because of the reusability of the moldhalves, a relatively high outlay can be expended at the time of theirproduction in order to obtain molds of extremely high precision andreproducibility. Since the mold halves do not touch each other in theregion of the lens to be produced, i.e. the cavity or actual moldingsurfaces, damage as a result of contact is ruled out. This ensures ahigh service life of the molds, which, in particular, also ensures highreproducibility of the contact lenses to be produced and high fidelityto the lens design.

In accordance with the invention, the lens formulation can be introduced(dispensed) into a cavity formed by a mold according to any knownmethods.

After the lens formulation is dispensed into the mold, it is polymerizedto produce a contact lens. Crosslinking may be initiated thermally orupon exposure to a light source including a light in a region between380 nm to 500 nm, preferably under a spatial limitation of actinicradiation, to crosslink the polymerizable components in the mixture.

In accordance with the invention, light source can be any ones emittinglight in the 380-500 nm range sufficient to activate Germane-basedNorrish Type I photoinitiators. Blue-light sources are commerciallyavailable and include: the Palatray CU blue-light unit (available fromHeraeus Kulzer, Inc., Irvine, Calif.), the Fusion F450 blue light system(available from TEAMCO, Richardson, Tex.), Dymax Blue Wave 200, LEDlight sources from Opsytec (385 nm, 395 nm, 405 nm, 435 nm, 445 nm, 460nm), LED light sources from Hamamatsu (385 nm), and the GE 24″ bluefluorescent lamp (available from General Electric Company, U.S.). Apreferred blue-light source is the UV LED from Opsytec (those describedabove).

The intensity of the light source is preferably from about 2 to about 40mW/cm², preferably from about 4 to about 20 mW/cm² in the 400 nm to 550nm region is more preferred. These intensity values are determined byweighting the lamp output using the photoinitiator master spectrum.

The photocrosslinking according to the invention may be effected in avery short time, e.g. in ≤about 120 seconds, preferably in ≤about 80seconds, more preferably in ≤50 about seconds, even more preferably in≤about 30 seconds, and most preferably in 4 to 30 seconds.

Opening of the mold so that the molded lens can be removed from the moldmay take place in a manner known per se.

The molded contact lens can be subject to lens extraction to removeunpolymerized vinylic monomers and macromers. The extraction solvent ispreferably water or an aqueous solution. After extraction, lenses can behydrated in water or an aqueous solution of a wetting agent (e.g., ahydrophilic polymer); packaged in lens packages with a packagingsolution which can contain about 0.005% to about 5% by weight of awetting agent (e.g., a hydrophilic polymer), a viscosity-enhancing agent(e.g., methyl cellulose (MC), ethyl cellulose, hydroxymethylcellulose,hydroxyethyl cellulose (HEC), hydroxypropylcellulose (HPC),hydroxypropylmethyl cellulose (HPMC), or a mixture thereof);sterilization such as autoclave at from 118 to 124° C. for at leastabout 30 minutes; and the like.

In a further aspect, the invention provides a hydrogel contact lenscomprising a crosslinked polymeric material which comprises repeatingunits of an UV-absorbing vinylic monomer of any one of formula (I) to(VII).

A contact lens of the invention preferably is characterized by having anUVB transmittance of about 10% or less (preferably about 5% or less,more preferably about 2.5% or less, even more preferably about 1% orless) between 280 and 315 nanometers and a UVA transmittance of about30% or less (preferably about 20% or less, more preferably about 10% orless, even more preferably about 5% or less) between 315 and 380nanometers and optionally (but preferably) a Violet transmittance ofabout 60% or less, preferably about 50% or less, more preferably about40% or less, even more preferably about 30% or less) between 380 nm and440 nm.

A contact lens of the invention further has a water content ofpreferably from about 15% to about 80%, more preferably from about 30%to about 70% by weight (at room temperature, about 22° C. to 28° C.)when fully hydrated.

Although various embodiments of the invention have been described usingspecific terms, devices, and methods, such description is forillustrative purposes only. The words used are words of descriptionrather than of limitation. It is to be understood that changes andvariations may be made by those skilled in the art without departingfrom the spirit or scope of the present invention, which is set forth inthe following claims. In addition, it should be understood that aspectsof the various embodiments may be interchanged either in whole or inpart or can be combined in any manner and/or used together, asillustrated below:

-   1. A UV-absorbing vinylic monomer of any one of formula (I) to (VII)

in which:

-   -   Rº is H or CH₃;    -   R₁, R₂ and R₂′ independent of one other are H, CH₃, CCl₃, CF₃,        Cl, Br, OH, OCH₃, or NR′R″ in which R′ and R″ independent of        each other are H or C₁-C₄ alkyl;    -   R₁′ independent of each other are H, CH₃, CCl₃, CF₃, Cl, Br, OH,        OCH₃, SO₃H, SO₃Na, or NR′R″ in which R′ and R″ independent of        each other are H or C₁-C₄ alkyl;    -   R₃ and R₄ independent of each other are H or a first hydrophilic        group which is *—CH₂—(OC₂H₄)_(n1)—OCH₃, *—CH₂—(OC₂H₄)_(n1)—OH,

-   -   provided that at least one of R₃ and R₄ is the first hydrophilic        group;    -   R₅ is H, *—COOH, *—CONH—C₂H₄—(OC₂H₄)_(n1)—OCH₃, or        *—CONH—C₂H₄—(OC₂H₄)_(n1)—OH;    -   one of R₆ and R₇ is H or a second hydrophilic group which is        *—CH₂—(OC₂H₄)_(n1)—OCH₃, *—CH₂—(OC₂H_(n1)—OH,

-   -   while the other of R₆ and R₇ is

-   -   R₈ is CH₃, C₂H₅,

-   -   R₉ is SO₃Na,

-   -   R₉′ is H, SO₃Na,

-   -   R₁₀ is methyl or ethyl;    -   L1 is a direct bond or a linkage of

-   -   L2 is a linkage of *—CH₂—*, *—C₂H₄—*, *—C₃H₆—*, *—C₃H₆—S—C₂H₄—*,        *—C₃H₆—S—C₃H₆—*, or

-   -   X1 is O or NRº; and    -   Y₁, Y₂, and Y₃ independent of one another are a C₂-C₄ alkylene        divalent radical;    -   Q1, Q2, and Q3 independent of one another are a        (meth)acryloylamido or (meth)acryloyloxy group;    -   m1 is zero or 1, provided that if m1 is zero, then Q₂ is a        (meth)acryloylamido group; and    -   n1 is an integer of 2 to 20 (preferably 3 to 15, more preferably        4 to 10).

-   2. The UV-absorbing vinylic monomer of invention 1, being a vinylic    monomer of formula (I).

-   3. The UV-absorbing vinylic monomer of invention 2, being selected    from a vinylic monomer of any one of the following formula:

in which: Q₁ is (meth)acryloylamido or (meth)acryloyloxy group; Y₁ is anethylene or propylene divalent radical; R₁ and R₂ independent of eachother are H, CH₃, CCl₃, CF₃, Cl, Br, OH, OCH₃, or NR′R″ in which R′ andR″ independent of each other are H, methyl or ethyl.

-   4. The UV-absorbing vinylic monomer of invention 1, being a vinylic    monomer of formula (II).-   5. The UV-absorbing vinylic monomer of invention 4, being selected    from a vinylic monomer of any one of the following formula:

in which: Q₁ is (meth)acryloylamido or (meth)acryloyloxy group; Y₁ is anethylene or propylene divalent radical; R₁ and R₂ independent of eachother are CH₃, CCl₃, CF₃, Cl, Br, NR′R″, OH, or OCH₃; R′ and R″independent of each other are H, methyl or ethyl; R₃ and R₄ independentof each other are *—CH₂—(OC₂H₄)_(n1)—OCH₃, *—CH₂—(OC₂H₄)_(n1)—OH,

R₁₀ is methyl or ethyl.

-   6. The UV-absorbing vinylic monomer of invention 1, being a vinylic    monomer of formula (III).-   7. The UV-absorbing vinylic monomer of invention 6, being selected    from a vinylic monomer of any one of the following formula:

in which: Q₁ is (meth)acryloylamido or (meth)acryloyloxy group; Y₁ is anethylene or propylene divalent radical; R₁ and R₂ independent of eachother are CH₃, CCl₃, CF₃, Cl, Br, NR′R″ OH, or OCH₃; in which R′ and R″independent of each other are H or C₁-C₄ alkyl; R₈ is CH₃, C₂H₅,

R₁₀ is methyl or ethyl.

-   8. The UV-absorbing vinylic monomer of invention 1, being a vinylic    monomer of formula (IV) or (V).-   9. The UV-absorbing vinylic monomer of invention 8, being selected    from a vinylic monomer of any one of the following formula:

in which R₁′ is H, CH₃, CCl₃, CF₃, Cl, Br, NR′R″ in which R′ and R″independent of each other are H or C₁-C₄ alkyl, OH, or OCH₃; Q₂ is(meth)acryloylamido or (meth)acryloyloxy group; Y₂ is an ethylene orpropylene divalent radical.

-   10. The UV-absorbing vinylic monomer of invention 1, being a vinylic    monomer of formula (VI) or (VII).-   11. The UV-absorbing vinylic monomer of invention 10, being selected    from a vinylic monomer of any one of the following formula:

in which R₁′ is H, CH₃, CCl₃, CF₃, Cl, Br, OH, or OCH₃, NR′R″ in whichR′ and R″ independent of each other are H or C₁-C₄ alkyl, R₈ is CH₃,C₂H₅,

R₁₀ is methyl or ethyl; Q₃ is (meth)acryloylamido or (meth)acryloyloxygroup; Y₃ is an ethylene or propylene divalent radical.

-   12. A hydrogel contact lens, comprising a crosslinked polymeric    material which comprises repeating units of a UV-absorbing vinylic    monomer of any one of inventions 1 to 11, wherein the hydrogel    contact lens has: an UVB transmittance (designated as UVB % T) of    about 10% or less between 280 and 315 nanometers; a UVA    transmittance (designated as UVA % T) of about 30% or less between    315 and 380 nanometers; and a water content of from about 15% to    about 80% by weight (at room temperature, about 22° C. to 28° C.)    when being fully hydrated.-   13. The hydrogel contact lens of invention 12, wherein the hydrogel    contact lens has an UVB % T of about 5% or less (preferably about    2.5% or less, more preferably about 1% or less) between 280 and 315    nanometers.-   14. The hydrogel contact lens of invention 12 or 13, wherein the    hydrogel contact lens has an UVA % T of about 20% or less    (preferably about 10% or less, more preferably about 5% or less)    between 315 and 380 nanometers.-   15. The hydrogel contact lens of any one of inventions 12 to 14,    wherein the hydrogel contact lens further has a Violet transmittance    (designated as Violet % T) of about 60% or less (preferably about    50% or less, more preferably about 40% or less, even more preferably    about 30% or less) between 380 nm and 440 nm.-   16. The hydrogel contact lens of any one of inventions 12 to 15,    wherein the hydrogel contact lens has a water content of from about    30% to about 75% by weight (at room temperature, about 22° C. to 28°    C.) when being fully hydrated.-   17. The hydrogel contact lens of any one of inventions 12 to 16,    wherein the hydrogel contact lens is a silicone hydrogel contact    lens, wherein the crosslinked polymeric material which comprises    repeating units of at least one hydrophilic vinylic monomer and    repeating units of at least one siloxane-containing vinylic monomer    and/or macromer.-   18. The hydrogel contact lens of any one of inventions 12 to 16,    wherein the crosslinked polymeric material which comprises repeating    units of an actinically-crosslinkable polyvinyl alcohol prepolymer.-   19. The hydrogel contact lens of invention 18, wherein the    actinically-crosslinkable polyvinyl alcohol prepolymer comprises    repeating units of vinyl alcohol

and repeating units of formula (VIII)

in which:

-   -   R₁₁ is hydrogen or C₁-C₆ alkyl;    -   R₁₂ is an ethylenically unsaturated group of

in which q1 and q2 independently of each another are zero or one, andR₁₆ and R₁₇ independently of each another are a C₂-C₈ alkylene divalentradical, R₁₈ is C₂-C₈ alkenyl;

-   -   R₁₃ can be hydrogen or a C₁-C₆ alkyl group; and    -   R₁₄ is a C₁-C₆ alkylene divalent radical.

-   20. The hydrogel contact lens of invention 19, wherein in    formula (VIII) R₁₁ is hydrogen or C₁-C₄ alkyl (preferably hydrogen    or methyl or ethyl, more preferably hydrogen or methyl).

-   21. The hydrogel contact lens of invention 19 or 20, wherein in    formula (VIII) R₁₃ is hydrogen.

-   22. The hydrogel contact lens of any one of inventions 19 to 21,    wherein in formula (VIII) R₁₄ is a C₁-C₄ alkylene divalent radical    (preferably methylene or butylene divalent radical, more preferably    methylene divalent radical).

-   23. A method for producing UV-absorbing contact lenses, comprising    the steps of:    -   (1) obtaining a lens formulation comprising        -   (a) a UV-absorbing vinylic monomer of any one of inventions            1 to 11,        -   (b) at least one free-radical initiator, and        -   (c) at least one polymerizable components selected from the            group consisting of a hydrophilic vinylic monomer, a            water-soluble silicone-free prepolymer, a            silicone-containing prepolymer, a non-silicone hydrophobic            vinylic monomer, a siloxane-containing vinylic monomer, a            siloxane-containing vinylic macromer, a vinylic crosslinking            agent, and combinations thereof;    -   (2) introducing the lens formulation into a mold for making a        soft contact lens, wherein the mold has a first mold half with a        first molding surface defining the anterior surface of a contact        lens and a second mold half with a second molding surface        defining the posterior surface of the contact lens, wherein said        first and second mold halves are configured to receive each        other such that a cavity is formed between said first and second        molding surfaces; and    -   (3) curing thermally or actinically the lens formulation in the        mold to form the UV-absorbing contact lens, wherein the formed        UV-absorbing contact lens is characterized by having the UVB % T        of about 10% or less between 280 and 315 nanometers and a UVA %        T of about 30% or less between 315 and 380 nanometers.

-   24. The method of invention 23, wherein the lens formulation    comprises from about 0.1% to about 4% by weight of, preferably from    about 0.2% to about 3.0% by weight of, more preferably from about    0.4% to about 2% by weight of, even more preferably from about 0.6%    to about 1.5% by weight of a UV-absorbing vinylic monomer of any one    of inventions 1 to 11.

-   25. The method of invention 23 or 24, wherein the lens formulation    comprises from about 0.1% to about 2.0% by weight of, preferably    from about 0.25% to about 1.75% by weight of, more preferably from    about 0.5% to about 1.5% by weight of, even more preferably from    about 0.75% to about 1.25% by weight of, at least one free-radical    initiator.

-   26. The method of any one of inventions 23 to 25, wherein the    free-radical initiator is a thermal initiator, wherein the step of    curing is carried out thermally.

-   27. The method of any one of inventions 23 to 25, wherein the    free-radical initiator is a photoinitiator, wherein the step of    curing is carried out by irradiation with a light having a    wavelength within the range from 380 nm to 500 nm.

-   28. The method of invention 27, wherein the photoinitiator is a    benzoylphosphine oxide.

-   29. The method of invention 27, wherein the photoinitiator is a    Germanium-based Norrish Type I photoinitiator.

-   30. The method of any one of inventions 23 to 27, wherein the lens    formulation comprises at least one hydrophilic vinylic monomer, at    least one siloxane-containing vinylic monomer, at least one    siloxane-containing vinylic macromer.

-   31. The method of any one of inventions 27 to 30, wherein the mold    is a reusable mold, wherein the step of curing is carried out by    using a spatial limitation of actinic radiation.

-   32. The method of any one of inventions 27 to 31, wherein the step    of curing lasts for a time period of about 120 seconds or less    (preferably about 80 seconds or less, more preferably about 50    seconds or less, even more preferably about 30 second or less, most    preferably from about 5 to about 30 seconds).

-   33. The method of any one of inventions 23 to 32, wherein the lens    formulation is a water-based lens formulation comprising at least    one actinically-crosslinkable polyvinyl alcohol prepolymer, wherein    the actinically-crosslinkable polyvinyl alcohol prepolymer comprises    repeating units of vinyl alcohol

and repeating units of formula (VIII)

in which:

-   -   R₁₁ is hydrogen or C₁-C₆ alkyl;    -   R₁₂ is an ethylenically unsaturated group of

in which q1 and q2 independently of each another are zero or one, andR₁₆ and R₁₇ independently of each another are a C₂-C₈ alkylene divalentradical, R₁₈ is C₂-C₈ alkenyl;

-   -   R₁₃ can be hydrogen or a C₁-C₆ alkyl group; and    -   R₁₄ is a C₁-C₆ alkylene divalent radical.

-   34. The method of invention 33, wherein in formula (VIII) R₁₁ is    hydrogen or C₁-C₄ alkyl (preferably hydrogen or methyl or ethyl,    more preferably hydrogen or methyl).

-   35. The method of invention 33 or 34, wherein in formula (VIII) R₁₃    is hydrogen.

-   36. The method of any one of inventions 33 to 35, wherein in    formula (VIII) R₁₄ is a C₁-C₄ alkylene divalent radical (preferably    methylene or butylene divalent radical, more preferably methylene    divalent radical).

-   37. The method of any one of inventions 33 to 36, wherein in    formula (VIII) R₁₁ is hydrogen or methyl, R₁₃ is hydrogen, and R₁₄    is methylene divalent radical.

-   38. The method of any one of inventions 23 to 37, wherein the formed    UV-absorbing contact lens has an UVB % T of about 5% or less    (preferably about 2.5% or less, more preferably about 1% or less)    between 280 and 315 nanometers.

-   39. The hydrogel contact lens of any one of inventions 23 to 38,    wherein the formed UV-absorbing contact lens has an UVA % T of about    20% or less (preferably about 10% or less, more preferably about 5%    or less) between 315 and 380 nanometers.

-   40. The hydrogel contact lens of any one of inventions 23 to 39,    wherein the hydrogel contact lens further has a Violet % T of about    60% or less (preferably about 50% or less, more preferably about 40%    or less, even more preferably about 30% or less) between 380 nm and    440 nm.

The previous disclosure will enable one having ordinary skill in the artto practice the invention. Various modifications, variations, andcombinations can be made to the various embodiment described herein. Inorder to better enable the reader to understand specific embodiments andthe advantages thereof, reference to the following examples issuggested. It is intended that the specification and examples beconsidered as exemplary.

Example 1

Transmittance.

Contact lenses are manually placed into a specially fabricated sampleholder or the like which can maintain the shape of the lens as it wouldbe when placing onto eye. This holder is then submerged into a 1 cmpath-length quartz cell containing phosphate buffered saline (PBS,pH˜7.0-7.4) as the reference. A UV/visible spectrophotometer, such as,Varian Cary 3E UV-Visible Spectrophotometer with a LabSphere DRA-CA-302beam splitter or the like, can be used in this measurement. Percenttransmission spectra are collected at a wavelength range of 250-800 nmwith % T values collected at 0.5 nm intervals. This data is transposedonto an Excel spreadsheet and used to determine if the lenses conform toClass 1 UV absorbance. Transmittance is calculated using the followingequations:

${{UVA}\mspace{14mu}\%\mspace{14mu} T} = {\frac{{Average}\mspace{14mu}\%\mspace{14mu} T\mspace{14mu}{between}\mspace{14mu} 380\text{-}316\mspace{14mu}{nm}}{{Luminescence}\mspace{14mu}\%\mspace{14mu} T} \times 100}$${{UVB}\mspace{14mu}\%\mspace{14mu} T} = {\frac{{Average}\mspace{14mu}\%\mspace{14mu} T\mspace{14mu}{between}\mspace{14mu} 280\text{-}315\mspace{14mu}{nm}}{{Luminescence}\mspace{14mu}\%\mspace{14mu} T} \times 100}$${{Violet}\mspace{14mu}\%\mspace{14mu} T} = {\frac{{Average}\mspace{14mu}\%\mspace{14mu} T\mspace{14mu}{between}\mspace{14mu} 440\text{-}380\mspace{14mu}{nm}}{{Luminescence}\mspace{14mu}\%\mspace{14mu} T} \times 100}$in which Luminescence % T is the average % transmission between 380 and780.Photo-Rheology:

The photo-rheology experiment measures the elastic (G′) and viscousmodulus (G″) as a function of time during curing. The experiment isconducted by using an appropriate light source, optionally cutofffilters to select wavelengths of interest, and a rheometer. The lightsource is a LED of appropriate wavelength (i.e. 385, 405, 435, 445, or460 nm), or Mercury bulb in a Hamamatsu light source. The intensity oflight source is set by adjusting either the light source output or theshutter opening to get an appropriate intensity measured by aradiometer. The sample is placed between a quartz plate that allows UVlight to pass through and the rheometer. The cure time is determinedwhen the elastic modulus (G′) reaches a plateau.

Example 2

This example illustrates how to prepare a preferred UV-absorbing vinylicmonomer of the invention according the procedures shown in the followingscheme.

Step 1—Synthesis of 2-acetyloxy-4-methoxy-4′-methyl-benzophenone

In a round bottom (rb) flask fitted with a stir bar and purged with drynitrogen (dN₂) was taken 80 g anhydrous tetrahydrofuran (THF, fromAldrich), 10 g (41.29 mmol/1.0 eq) of2-hydroxy-4-methoxy-4′-methylbenzophenone (HO-MeO-Me-Bzp) (from AlfaAesar) (compound I) and 0.25 g of N,N-dimethyamino pyridine (DMAP) (5mol % with respect to [wrt] to compound I from Alfa Aesar). About 5 mLdry THF was used to rinse the DMAP vial and then this was added to thereaction flask. The mixture was stirred at room temperature (RT) todissolve over 15 mins. Then, 26 g (6 eq) of triethylamine (TEA, fromAldrich) was added via a syringe. The solution was stirred at RT for 15minutes. Then, 13.17 g (3.1 eq) Acetic anhydride (Ac2O) was added slowlyto the reaction mixture over 5 minutes. 15 mL of anhydrous THF was addedto the flask. The reaction solution was stirred under nitrogen (N₂) atRT, overnight and then was concentrated under reduced pressure to removeabout 80% of the volatiles. THF was added to make a total solution masshaving a concentration of about 30 wt % wrt starting benzophenone. Thesolution was stirred at RT for 5 mins. The product was precipitated byslow addition of a 150 g mixture of 1:1 ice:water (5× by weight [wt] ofreaction solution) with stirring. The flask was place in ice water bathand stirred for 3 hours. After 3 hours, the pH of the solution phase wasmeasured as 3.86 (pH meter) and the mixture was filtered through aWhatman#4 (25 μm) filter paper under vacuum of 940 mbar. The precipitatewas washed with about 1500 g of ice cold water until the washings wereclear colorless and the conductivity of the filtrate was <10 μS/cm andpH neutral. The precipitate was collected and was suspended in 100 mLcold DI Water and swirled for 15 mins. The obtained product was thenfrozen in IPA-dry ice and then lyophilized. A white powder was obtainedthat was weighed (Net: 11.45 g; Th Yield: 11.77 g; Yield: 97.36%) andwas confirmed by 1H-NMR in THF-d8 to be2-acetyloxy-4-methoxy-4′-methylbenzophenone (AcO-MeO-Me-Bzp) (compoundII).

Step 2—Synthesis of 2-acetyloxy-4-methoxy-4′-bromomethyl-benzophenone

Acetonitrile, N-Bromosuccinimide (NBS) and AIBN were purchased fromSigma Aldrich and acetate protected benzophenone derivative (II) wasused as obtained from the previous step. In a 500 mL 3-neck flask fittedwith condenser, a N₂ purge set up, a thermocouple, an oil-bubbler airtrap and a stir bar was added 8.85 g (0.031 mol/1.0 eq) ofAcO-MeO-Me-Bzp (II) obtained in Step 1 and was stirred under N₂ for 30mins. The condenser was set to 9° C. and 220 mL of anhydrousacetonitrile was added to the reaction flask. The mixture was stirred atRT. Once the condenser had reached around 9° C., the reaction flask wasgently purged with dry N₂ for 30 mins and the condenser was set to 4° C.After condenser had reached 4° C. or 30 mins of N₂ purge (whichever islater), the reaction mixture was quickly raised to reflux at 400 rpmstirring and with a mildly positive N₂ flow. The reaction solution cameto reflux at ˜80-82° C. Then 6.11 g (1.1 eq.) of N-Bromosuccinimide(NBS) (from Sigma-Aldrich) and 0.52 g (0.1 eq.) ofAza-bis-isobutyronitrile (from Sigma-Aldrich) were weighed out and addedto the reaction flask under positive N₂ flow. The reaction wascontinued, at reflux for 2 h with mildly positive nitrogen flow. Aftertwo hours the reaction was stopped by being allowed to cool to RT undervery mild flow of dry N₂. The cooled reaction solution was filteredthrough a cotton plug. The solution was then concentrated to about 50 wt% under reduced pressure. The product was precipitated form the reactionsolution by addition of about 200 g of 1:1 ice-water mixture (about 3×the reaction solution wt.).

The mixture was stirred in an ice bath for 3 hours. After three hoursthe precipitate was filtered through a Whatman #4 (25 μm) filter paperunder 950 mbar pressure. The precipitate was washed 5× with 200 mL coldDI Water, (˜5× volume of ice-water used for pptn) until the conductivityof the filtrate was less than 10 uS/cm and neutral pH. The solid samplewas mixed with 100 mL cold DI Water and the mixture was then frozen indry-ice/IPA bath and then lyophilized. A powdery off white solid wasobtained (Net: 10.986 g; Th Y: 11.307 g; % Y; 97.17%) and confirmed byNMR to be product III, 2-acetyloxy-4-methoxy-4′-bromomethyl-benzophenone(AcO-MeO—BrCH₂-Bzp). The % purity of product III was estimated from NMRto be 85 mol % with about 7% likely to be unreacted starting materialand about 8% other unidentified impurities.

Step 3—Synthesis of2-acetyloxy-4-methoxy-4′-(acrylamido-N,N-dimethypropylaminomethyl)-benzophenone

In a weighed 20 mL amber glass vial with stir bar was taken 1.5 g (0.004mol/1 eq) of product (III) from Step 2, AcO-MeO—BrCH₂-Bzp. To this wasadded 8 mL ethyl acetate with stirring for 10 mins at room temperature(RT). To the obtained solution was added 1.94 g (0.0123 mol/3. eq) ofN,N-dimethylaminopropyl acrylamide (NN-DMAPrAAm) at RT with stirring. Aprecipitate slowly formed and the reaction was stirred at RT overnight.To the reaction mixture was added 1 mL of hexane and the reactionmixture stirred for an hour at RT. The clear supernatant was discarded.The residue was dissolved in 0.50 mL acetonitrile and stirred for 30mins to dissolve. The product in the solution was precipitated usingexcess 1:1 Ethyl acetate:hexane mixture. The process is repeated 4times. To the solid residue obtained was added 5 mL DI Water and themixture allowed to dissolve. MEHQ was added to make a concentration of˜150 mg/Kg (ppm) based on estimated final product weight. The residualorganics from the cloudy solution were removed under reduced pressure togive a clear solution having neutral pH. The solution was frozen andlyophilized overnight. Net: 1.4829 g; Th.Y: 2.05 g; % Y; 72.19%. Thebulk sample was deliquescent and was flushed with dry air and stored ina dessicator in the amber flask. The product IV was obtained andestimated from NMR to have a purity of >90%.

Step 4—Synthesis of2-hydroxy-4-methoxy-4′-(acrylamido-N,N-dimethypropylaminomethyl)-benzophenone

A 5.0 mL solution of acetate protected UV-blocker (IV) in DI Water at1000 mg/L was prepared. This solution was diluted to 20 mg/L with pH7buffer (12.5 mM phosphate in DI Water:n-propanol). The UV-Vis spectrumof this solution was collected (FIG. 1, Curve 1).

Solid Potassium Carbonate (K₂CO₃) was added to the 1000 mg/L solution tohave a K₂CO₃ concentration of 1 w/v %. The solution was mixed todissolve the K₂CO₃ and the solution was allowed to stand overnight at RTto obtain the desired product (UV-absorbing vinylic monomer, i.e.,compound V in the scheme). The resultant solution was diluted to have aconcentration of 20 mg/L for the UV-absorbing vinylic monomer with pH7buffer (12.5 mM phosphate in DI Water:n-propanol). The UV-Vis spectrumof this solution of the UV-absorbing vinylic monomer was collected andis shown in FIG. 1 (curve 2).

Example 3

The UV-absorbing vinylic monomer prepared in Example 2 was directlyadded to an aqueous lens formulation, which is described in Example 8-8dof WO2002071106 (herein incorporated by reference in its entirety), at aconcentration of 0, 0.7 and 1.5 wt % and each having 1.0 wt % Lithiumsalt of 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (Li-TPO) (fromTCI-America,

as the photoinitiator. Those three formulations are determined by photorheology studies (405 nm LED source at 30 mW/cm²) to have a curing timeof about 21 seconds, about 23 seconds, or about 21 seconds respectively.

Lenses were fabricated from those aqueous formulations according to anautomated lens manufacturing process described in Example 8 ofWO2002071106 except that a lens formulation in a mold is irradiated with405 nm LED at an intensity of 30 mW/cm² for about 25 seconds. Theresultant lenses were packaged in blister packages containing Saline 61,sealed and autoclaved at 121° C. for 45 mins. The % T (percentagetransmittance) of the autoclaved lenses was determined. Where theconcentration of the UV-absorbing vinylic monomer is 0 (i.e., controllenses), the control lenses have a % T-UVA˜96.30% and a % T-UVB˜84.61%.Where the concentration of the UV-absorbing vinylic monomer is 0.70% byweight, the resultant lenses have a % T-UVA˜23.6% and a % T-UVB˜3.79%.Where the concentration of the UV-absorbing vinylic monomer is 1.50% byweight, the resultant lenses have a % T-UVA˜8.80% and a % T-UVB˜0.13%.

FIGS. 2 and 3 show the % T of the lenses having 0.7 wt % and 1.5 wt % ofthe UV-absorbing vinylic monomer after autoclave along with controllenses (0 wt % of the UV-absorbing vinylic monomer) after autoclave.

Example 4

This example illustrates how to prepare a preferred UV-absorbing vinylicmonomer of the invention according to the following scheme.

Step 1—Synthesis of 2-(2-acetyloxy-5-methylphenyl)benzotriazole(AcO-Me-Bzt)

In a weighed 2 L rb flask fitted with a magnetic stir bar and purgedwith N₂ is added 340 g anhydrous THF. The flask is purged with N₂ for aminute while stirring and then capped. 40 g (177.4 mmol, 1.0 eq) of2-(2-Hydroxy-5-methylphenyl)benzotriazole (Me-Bzt-OH, from TCI-America)is weighed and added to the flask. The reaction flask is quickly purgedwith N₂ and then capped and stirred to allow the solid to dissolve. Tothis solution is added 1.09 g (8.87 mmol) of 4-dimethylaminopyridine(4-DMAP) (5 mol % wrt benotriazole). The flask is quickly purged withN₂, capped and the reaction mixture is allowed to stir to allow thesolid to dissolve. 108.96 g (6 eq) of Triethyl amine (Et₃N) is weighedout and slowly added to the reaction flask with stirring. 54.58 g (3 eq)of Ac₂O is weighed out and then slowly added to the reaction solution.20 g of THF is added to the reaction. The flask is purged with N₂,capped tightly and the reaction solution is allowed stir under N₂overnight.

The reaction solution is concentrated under reduced pressure, to remove˜65-70% of the volatiles or until precipitation is observed, whicheveris earlier. If precipitation is seen, just enough THF is added to justdissolve the precipitate. The solution is stirred at RT for 30 mins. Theproduct is precipitated by addition of a mixture of 250 g ice and 250 gDI Water with stirring. The obtained mixture had a pH of 4.75. The flaskis place in an ice bath and stirred for 3 hours. The mixture is filteredthrough a Whatman #4 (25 um) filter paper under vacuum of 950 mbar. Theprecipitate is washed five times with 1 Kg of ice-water until thewashings are clear colorless and the conductivity of the filtrate is <10uS/cm. The precipitate is collected and mixed with 500 mL cold DI water.The mixture is frozen and then lyophilized to give a white powder (47.22g) whose structure is confirmed by NMR to be AcO-Me-Bzt. Net: 47.22 g;Th Yield: 47.29 g; Yield: 99.85%; Purity: >90%.

Step 2—Synthesis of 2-(2-acetyloxy-5-bromomethylphenyl)benzotriazole(AcO—BrCH₂-Bzt)

In a 1 L 3-neck flask fitted with condenser, a N₂ purge set up, athermocouple and an oil-bubbler air trap was added 20 g (0.074 mmol/1.0eq) of AcO-Me-Bzt (II) from Step 2. This solid was stirred under N₂ forat least 45 mins. To this was added 480 mL of anhydrous acetonitrile andthe mixture was stirred at RT under N₂ to effect a solution. Thecondenser was set to 9° C. and the reaction solution was gently bubbledwith dry N₂ for 30 mins. After condenser had reached 4° C. or 30 mins ofN₂ purge (whichever is later), the reaction mixture was quickly raisedto reflux, stirred at 400 rpm with a slightly positive N₂ flow. Thereaction solution came to reflux at ˜81-82° C. 14.71 g (1.1 eq) of NBSand 1.25 g (0.1 eq) of AIBN were added to the reaction flask underpositive N₂ flow and the reaction were allowed to continue at refluxunder a slightly positive N₂ flow. After 2 h 15 m the reaction wasstopped by being allowed to cool to RT under N₂. The reaction solutionwas filtered through a cotton plug into a 1 L rb flask. The solution wasthen concentrated under reduced pressure to yield a solid material. Tothe sample was added 75 mL of 6.67% ACN in THF to dissolve the solid.About 250 g of 1:1 ice-water by weight was prepared (˜2.5× the totalsolution volume). The product was precipitated by slow addition of theice-water mixture with stirring. The flask was then placed in an icebath and stirred for 3 hours. The precipitate was filtered through aWhatman #4 (25 um) filter paper under mild vacuum. The precipitate waswashed 5× with 500 mL cold DI Water. (˜10× volume of ice-water used forprecipitation) until the conductivity of the filtrate was <10 uS/cm andneutral pH. The solid sample obtained was transferred to a 1 L rb flaskand mixed 100 mL cold DI Water. The mixture was then frozen and thenlyophilized to give a solid product (Net: 26.08 g; Th. yield: 25.83 g; %Yield: >100%; purity: 75% with 10% likely to be unreacted startingmaterial and 15% unidentified material).

Step 3—Synthesis of Compound IV

In weighed amber 1 L flask with stir bar was taken 22 g (0.058 mol/1 eq)of product (III) (AcO—BrCH₂-Bzt), assuming 92% purity based on NMR. Tothis was added 350 mL ethyl acetate (EtAc) to dissolve. The solution wasstirred at RT for an hour. During this time 27.592 g/0.176 mol/3 eq ofNN-DMAPrAAm was measured out in a 50 mL dropping funnel. The NN-DMAPrAAmwas slowly added to the reaction solution dropwise over 15 minutes at RTwith stirring. A precipitate slowly began to form and the reaction wasstirred at RT overnight, covered in foil. The stirring was stopped andthe precipitate was allowed to settle. The supernatant was decanted fromthe reaction solution to give 70.4 g of a solid. To this was added 70 mLacetonitrile and the mixture swirled for an hour in a foil covered flaskat RT, to dissolve. The resulting solution was concentrated underreduced pressure to remove 80% of the volatiles. To the solution wasslowly added 120 mL of 16.7% hexane in EtAc with stirring, to give a2-phase mixture. The clear supernatant was decanted to give about 30 gof a viscous semi-solid. To the viscous residue was added 60 mL ofacetonitrile and swirled for 15 mins to dissolve the residue and thenconcentrated under reduced pressure to remove 90-95% of the volatiles. Aclear viscous liquid was obtained. To this was added 120 mL of 16.67%hexane in Ethyl acetate solution using a dropping funnel with stirring.Two phases were observed a lower viscous paste-like solid and upper hazysupernatant phase. The mixture was stirred gently at RT for 15 mins andthen allowed to stand for 45 mins. The clear colorless supernatant wasdecanted to yield about 32 g of a viscous semi-solid. This process wasrepeated twice more to yield a viscous semi-solid reside. The volatilesfrom the crude residue were removed under reduced pressure to give about25 g of solid material. MEHQ, 3.7 mg, was dissolved in Acetonitrile andadded to the residue (˜150 mg/Kg (ppm) MEHQ based on estimated productweight). About 50 mL of acetonitrile was added to the residue and themixture swirled to dissolve over 15 minutes. The solution wasconcentrated in an amber flask under reduced pressure to remove as muchof the volatiles as possible to give 21.21 g of a solid mass. To theresidue was added 200 g DI Water and the mixture were stirred for 10minutes. The sample was gravity filtered, in the dark, through aWhatman#5 (2.5 um) filter paper, to give a clear solution having neutralpH. This clear solution was frozen and lyophilized to give an off-whitesolid. Total Yield 18 g % Yield: 77%.

Step 4—Synthesis of Compound V (UV-Absorbing Vinylic Monomer Having aBenzotriazole Moiety)

A 5.0 mL solution of product IV in DI Water at a concentration of 1000mg/L was prepared. This aqueous solution was diluted to 20 mg/L with pH7buffer (12.5 mM phosphate in DI Water:n-propanol). The UV-Vis spectrumof this solution was collected (FIG. 4, Curve 1).

Solid potassium carbonate (K₂CO₃) was added to the 1000 mg/L solution tohave a K₂CO₃ concentration of 1 w/v %. The solution was mixed todissolve the K₂CO₃ and the solution was allowed to stand overnight at RTto obtain the desired product—UV-absorbing vinylic monomer (i.e.,compound V in the scheme). The resultant solution was diluted to 20 mg/Lof the UV-absorbing vinylic monomer with pH7 buffer (12.5 mM phosphatein DI Water:n-propanol). The UV-Vis spectrum of this solution of theUV-absorbing vinylic monomer was collected and is shown in FIG. 4 (Curve2).

Example 5

The UV-absorbing vinylic monomer prepared in Example 4 was directlyadded to an aqueous lens formulation, which is described in Example 8-8dof WO2002071106 (herein incorporated by reference in its entirety), at aconcentration of 0, 0.91 wt % and 1.4 wt % and each having 1.0 wt %Li-TPO as the photoinitiator. Those three formulations are determined byphoto rheology studies (405 nm LED source at 30 mW/cm²) to have a curingtime of about 25 seconds, about 60 seconds, or about 82 secondsrespectively.

Lenses were fabricated from those aqueous formulations according to anautomated lens manufacturing process described in Example 8 ofWO2002071106 except that a lens formulation in a mold is irradiated with405 nm LED at an intensity of 30 mW/cm² for about 25 seconds. Theresultant lenses were packaged in blister packages containing Saline 61,sealed and autoclaved at 121° C. for 45 mins. The % T of the autoclavedlenses was determined. Where the concentration of the UV-absorbingvinylic monomer is 0 (i.e., control lenses), the control lenses have a %T-UVA˜95.57% and a % T-UVB˜81.64%. Where the concentration of theUV-absorbing vinylic monomer is 0.91% by weight, the resultant lenseshave a % T-UVA˜7.39% and a % T-UVB˜2.74%. Where the concentration of theUV-absorbing vinylic monomer is 1.40% by weight, the resultant lenseshave a % T-UVA˜3.45% and a % T-UVB˜0.59%.

FIGS. 5 and 6 show the % T of the lenses having 0.91 wt % and 1.4 wt %of the UV-absorbing vinylic monomer after autoclave along with controllenses (free of the UV-absorbing vinylic monomer) after autoclave.

What is claimed is:
 1. A UV-absorbing vinylic monomer of any one offormula (I) to (VII)

in which: R₂ and R₂′ independent of one other are H, CH₃, CCl₃, CF₃, Cl,Br, OH, OCH₃, or NR′R″ in which R′ and R″ independent of each other areH or C₁-C₄ alkyl; R₁′ independent of each other are H, CH₃, CCl₃, CF₃,Cl, Br, OH, OCH₃, SO₃H, SO₃Na, or NR′R″ in which R′ and R″ independentof each other are H or C₁-C₄ alkyl; R₉ is SO₃Na,

R₉′ is H, SO₃Na,

R₁₀ is methyl or ethyl; L1 is a direct bond or a linkage of

L2 is a linkage of

X1 is O or NRº; and Y₂, and Y₃ independent of one another are a C₂-C₄alkylene divalent radical; Q2, and Q3 independent of one another are a(meth)acryloylamido or (meth)acryloyloxy group; m1 is zero or 1,provided that if m1 is zero, then Q₂ is a (meth)acryloylamido group. 2.The UV-absorbing vinylic monomer of claim 1, being a vinylic monomer offormula (IV) or (V).
 3. The UV-absorbing vinylic monomer of claim 2,being selected from a vinylic monomer of any one of the followingformula:

in which R₁′ is H, CH₃, CCl₃, CF₃, Cl, Br, NR′R″ in which R′ and R″independent of each other are H or C₁-C₄ alkyl, OH, or OCH₃; Q₂ is(meth)acryloylamido or (meth)acryloyloxy group; Y₂ is an ethylene orpropylene divalent radical.
 4. The UV-absorbing vinylic monomer of claim1, being a vinylic monomer of formula (VI) or (VII).
 5. The UV-absorbingvinylic monomer of claim 4, being selected from a vinylic monomer of anyone of the following formula:

in which R₁′ is H, CH₃, CCl₃, CF₃, Cl, Br, OH, or OCH₃, NR′R″ in whichR′ and R″ independent of each other are H or C₁-C₄ alkyl, R₈ is CH₃,C₂H₅,

R₁₀ is methyl or ethyl; Q₃ is (meth)acryloylamido or (meth)acryloyloxygroup; Y₃ is an ethylene or propylene divalent radical.